Nonlinear Semiclassical Spectroscopy of Ultrafast Molecular Polariton Dynamics

We introduce a theoretical framework that allows for the systematic and efficient description of the ultrafast nonlinear response of molecular polaritons, i.e., hybrid light-matter states, in the collective regime of large numbers of molecules N coupled to the cavity photon mode. Our approach is based on a semiclassical, mean-field evolution of the molecular Hamiltonian and the cavity field, which is complemented by a perturbative expansion of both light and matter counterparts in the input fields entering the cavity. In addition, expansion in terms of the pulse phases enables us to disentangle different excitation pathways in Liouville space, thereby distinguishing contributions to the nonlinear response. The formalism extends traditional free-space nonlinear spectroscopy by incorporating the feedback of matter onto the light field via the induced polarization. We demonstrate the utility of the framework by applying it to the calculation of pump-probe polariton spectra and show how, by storing the pulses, the cavity facilitates additional excitation pathways, which can be used to isolate purely bright state contributions. Our method, which does not scale with N, is broadly applicable and can be extended to model a wide range of current experiments investigating the dynamical nonlinear response of hybrid light-matter states.